Interlayer Slipping Facilitating Manipulation of Electronic Properties of Few-Layer Two-Dimensional Conjugated Polymers

Abstract

Two-dimensional conjugated polymers (2DCPs) have received great interest in smart devices due to their unique physical properties associated with flexibility, nanosized thickness, and correlated quantum size effect. Control of interlayer interactions of multilayer 2DCPs is crucial for modulating the confinement of charge carriers, heat, and photons to give remarkable properties because of the breaking of symmetry. However, to date, it is unclear how the multilayers of 2DCPs affect their physical properties. In this article, we for the first time perform a density functional theory calculation for the interlayer slipping effect on in-plane electronic properties of few-layer 2DCPs. Based on five homopolymers formed by C─C bonds with various stacking configurations beyond the inclined and serrated ones, results show that a moderate electric field causes the valence (conduction) band of few-layer 2DCPs to exhibit distinctive electrical characteristics which are dominated by the outermost two layers on hole (electron) enriched side. Analysis based on recombined molecular orbitals reveals that band properties are sensitive to the interlayer offsets when they result from the interference among multiple orbitals from each building block. This result provides a new guideline for manipulating charge transfer and spintronic properties of few-layer 2DCPs through an electric field to advance their various applications.

Keywords

density functional theory / interference / interlayer interactions / two-dimensional conjugated polymers

References

[1] X. Zhang, C. Liu, Y. Tao, et al., “High ZT 2D Thermoelectrics by Design: Strong Interlayer Vibration and Complete Band-Extrema Alignment,” Advanced Functional Materials 30, no. 22 (2020): 2001200.

[2] R. Longuinhos and J. Ribeiro-Soares, “Stable Holey Two-Dimensional C₂N Structures With Tunable Electronic Structure,” Physical Review B 97, no. 19 (2018): 195119.

[3] R. Bistritzer and A. H. MacDonald, “Moiré Bands in Twisted Double-Layer Graphene,” Proceedings of the National Academy of Sciences 108, no. 30 (2011): 12233–12237.

[4] Y. Cao, V. Fatemi, A. Demir, et al., “Correlated Insulator Behaviour at Half-Filling in Magic-Angle Graphene Superlattices,” Nature 556, no. 7699 (2018): 80–84.

[5] R. Zhang, B. Li, and J. Yang, “Effects of Stacking Order, Layer Number and External Electric Field on Electronic Structures of Few-Layer C₂N-h2D,” Nanoscale 7, no. 33 (2015): 14062–14070.

[6] M. E. Foster, K. Sohlberg, M. D. Allendorf, and A. A. Talin, “Unraveling the Semiconducting/Metallic Discrepancy in Ni₃(HITP)₂,” Journal of Physical Chemistry Letters 9, no. 3 (2018): 481–486.

[7] Y. Wang, Q. Zhang, X.-Z. Li, et al., “Highly Fluorescent Semiconducting Two-Dimensional Conjugated Polymer Films Achieved by Side-Chain Engineering Showing Large Exciton Diffusion Length,” CCS Chemistry 5, no. 10 (2023): 2366–2377.

[8] M. A. Springer, T. J. Liu, A. Kuc, and T. Heine, “Topological Two-Dimensional Polymers,” Chemical Society Reviews 49, no. 7 (2020): 2007–2019.

[9] Z. Zhang, Q. Liu, H. Dong, and W. Hu, “Conjugated Polymer Crystals via Topochemical Polymerization,” Science China Chemistry 62, no. 10 (2019): 1271–1274.

[10] Y. Li, Q. Wu, X. Guo, et al., “Laminated Self-Standing Covalent Organic Framework Membrane With Uniformly Distributed Subnanopores for Ionic and Molecular Sieving,” Nature Communications 11, no. 1 (2020): 599.

[11] Z. Meng, R. M. Stolz, and K. A. Mirica, “Two-Dimensional Chemiresistive Covalent Organic Framework With High Intrinsic Conductivity,” Journal of the American Chemical Society 141, no. 30 (2019): 11929–11937.

[12] H. Chen, S. Zhang, W. Jiang, et al., “Prediction of Two-Dimensional Nodal-Line Semimetals in a Carbon Nitride Covalent Network,” Journal of Materials Chemistry A 6, no. 24 (2018): 11252–11259.

[13] Z. Zhou, L. Zhang, Y. Yang, et al., “Growth of Single-Crystal Imine-Linked Covalent Organic Frameworks Using Amphiphilic Amino-Acid Derivatives in Water,” Nature Chemistry 15, no. 6 (2023): 841–847.

[14] F. Auras, L. Ascherl, A. H. Hakimioun, et al., “Synchronized Offset Stacking: A Concept for Growing Large-Domain and Highly Crystalline 2D Covalent Organic Frameworks,” Journal of the American Chemical Society 138, no. 51 (2016): 16703–16710.

[15] S. Tao, L. Zhai, A. D. Dinga Wonanke, M. A. Addicoat, Q. Jiang, and D. Jiang, “Confining H₃PO₄ Network in Covalent Organic Frameworks Enables Proton Super Flow,” Nature Communications 11, no. 1 (2020): 1981.

[16] W. Jiang, X. Ni, and F. Liu, “Exotic Topological Bands and Quantum States in Metal-Organic and Covalent-Organic Frameworks,” Accounts of Chemical Research 54, no. 2 (2021): 416–426.

[17] X. Li, P. Yadav, and K. P. Loh, “Function-Oriented Synthesis of Two-Dimensional (2D) Covalent Organic Frameworks−From 3D Solids to 2D Sheets,” Chemical Society Reviews 49, no. 14 (2020): 4835–4866.

[18] M. D. Allendorf, R. Dong, X. Feng, S. Kaskel, D. Matoga, and V. Stavila, “Electronic Devices Using Open Framework Materials,” Chemical Reviews 120, no. 16 (2020): 8581–8640.

[19] C. Li, Y. Wang, Y. Zou, X. Zhang, H. Dong, and W. Hu, “Two-Dimensional Conjugated Polymer Synthesized by Interfacial Suzuki Reaction: Towards Electronic Device Applications,” Angewandte Chemie International Edition 59, no. 24 (2020): 9403–9407.

[20] Y. Fan, Q. Wen, T. G. Zhan, Q. Y. Qi, J. Q. Xu, and X. Zhao, “A Case Study on the Influence of Substitutes on Interlayer Stacking of 2D Covalent Organic Frameworks,” Chemistry – A European Journal 23, no. 24 (2017): 5668–5672.

[21] L. M. Salonen, D. D. Medina, E. Carbó-Argibay, et al., “A Supramolecular Strategy Based on Molecular Dipole Moments for High-Quality Covalent Organic Frameworks,” Chemical Communications 52, no. 51 (2016): 7986–7989.

[22] J. Tan, W. Weng, J. Zhu, et al., “A Phosphine-Amine-Linked Covalent Organic Framework With Staggered Stacking Structure for Lithium-Ion Conduction,” Angewandte Chemie International Edition 62, no. 52 (2023): e202310972.

[23] C. E. Pelkowski, A. Natraj, C. D. Malliakas, et al., “Tuning Crystallinity and Stacking of Two-Dimensional Covalent Organic Frameworks Through Side-Chain Interactions,” Journal of the American Chemical Society 145, no. 40 (2023): 21798–21806.

[24] L. Ascherl, T. Sick, J. T. Margraf, et al., “Molecular Docking Sites Designed for the Generation of Highly Crystalline Covalent Organic Frameworks,” Nature Chemistry 8, no. 4 (2016): 310–316.

[25] Z. Shan, M. Wu, T. Liu, et al., “Adjusting the Stacking Model of Two-Dimensional Covalent Organic Frameworks for Volatile Acid Sensing via Spatial Effects,” ACS Applied Materials & Interfaces 15, no. 29 (2023): 35350–35357.

[26] J. Liu, P. Lyu, Y. Zhang, P. Nachtigall, and Y. Xu, “New Layered Triazine Framework/Exfoliated 2D Polymer With Superior Sodium-Storage Properties,” Advanced Materials 30, no. 11 (2018): 1705401.

[27] Z. Wang, Y. Zhang, T. Wang, et al., “Modulating the Interlayer Stacking of Covalent Organic Frameworks for Efficient Acetylene Separation,” Small 19, no. 32 (2023): 2303684.

[28] S. Cai, B. Sun, X. Li, et al., “Reversible Interlayer Sliding and Conductivity Changes in Adaptive Tetrathiafulvalene-Based Covalent Organic Frameworks,” ACS Applied Materials & Interfaces 12, no. 16 (2020): 19054–19061.

[29] C. Kang, Z. Zhang, V. Wee, et al., “Interlayer Shifting in Two-Dimensional Covalent Organic Frameworks,” Journal of the American Chemical Society 142, no. 30 (2020): 12995–13002.

[30] Y. Zhang, M. Položij, and T. Heine, “Statistical Representation of Stacking Disorder in Layered Covalent Organic Frameworks,” Chemistry of Materials 34, no. 5 (2022): 2376–2381.

[31] C. Winkler, T. Kamencek, and E. Zojer, “Understanding the Origin of Serrated Stacking Motifs in Planar Two-Dimensional Covalent Organic Frameworks,” Nanoscale 13, no. 20 (2021): 9339–9353.

[32] M. Gray and J. M. Herbert, “Origins of Offset-Stacking in Porous Frameworks,” Journal of Physical Chemistry C 127, no. 5 (2023): 2675–2686.

[33] K. S. Rawat, S. Borgmans, T. Braeckevelt, C. V. Stevens, P. van der Voort, and V. van Speybroeck, “How the Layer Alignment in Two-Dimensional Nanoporous Covalent Organic Frameworks Impacts Its Electronic Properties,” ACS Applied Nano Materials 5, no. 10 (2022): 14377–14387.

[34] A. Kuc, M. A. Springer, K. Batra, R. Juarez-Mosqueda, C. Wöll, and T. Heine, “Proximity Effect in Crystalline Framework Materials: Stacking-Induced Functionality in MOFs and COFs,” Advanced Functional Materials 30, no. 41 (2020): 1908004.

[35] J. Huang, M. J. Golomb, S. R. Kavanagh, K. Tolborg, A. M. Ganose, and A. Walsh, “Band Gap Opening From Displacive Instabilities in Layered Covalent-Organic Frameworks,” Journal of Materials Chemistry A 10, no. 25 (2022): 13500–13507.

[36] B. Lukose, A. Kuc, J. Frenzel, and T. Heine, “On the Reticular Construction Concept of Covalent Organic Frameworks,” Beilstein Journal of Nanotechnology 1, no. 1 (2010): 60–70.

[37] W. Zhou, H. Wu, and T. Yildirim, “Structural Stability and Elastic Properties of Prototypical Covalent Organic Frameworks,” Chemical Physics Letters 499, no. 1–3 (2010): 103–107.

[38] B. T. Koo, W. R. Dichtel, and P. Clancy, “A Classification Scheme for the Stacking of Two-Dimensional Boronate Ester-Linked Covalent Organic Frameworks,” Journal of Materials Chemistry 22, no. 34 (2012): 17460.

[39] E. L. Spitler, B. T. Koo, J. L. Novotney, et al., “A 2D Covalent Organic Framework With 4.7-nm Pores and Insight Into Its Interlayer Stacking,” Journal of the American Chemical Society 133, no. 48 (2011): 19416–19421.

[40] A. M. Pütz, M. W. Terban, S. Bette, F. Haase, R. E. Dinnebier, and B. V. Lotsch, “Total Scattering Reveals the Hidden Stacking Disorder in a 2D Covalent Organic Framework,” Chemical Science 11, no. 47 (2020): 12647–12654.

[41] I. A. Moses and V. Barone, “Structural and Electronic Properties of Layered Nanoporous Organic Nanocrystals,” RSC Advances 11, no. 10 (2021): 5773–5784.

[42] M. Bieri, M. Treier, J. Cai, et al., “Porous Graphenes: Two-Dimensional Polymer Synthesis With Atomic Precision,” Chemical Communications 45, no. 45 (2009): 6919–6921.

[43] M. Bieri, M. T. Nguyen, O. Gröning, et al., “Two-Dimensional Polymer Formation on Surfaces: Insight Into the Roles of Precursor Mobility and Reactivity,” Journal of the American Chemical Society 132, no. 46 (2010): 16669–16676.

[44] D. Zhou, X. Tan, H. Wu, L. Tian, and M. Li, “Synthesis of C−C Bonded Two-Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid-Liquid Interface,” Angewandte Chemie International Edition 58, no. 5 (2019): 1376–1381.

[45] C. Steiner, J. Gebhardt, M. Ammon, et al., “Hierarchical On-Surface Synthesis and Electronic Structure of Carbonyl-Functionalized One- and Two-Dimensional Covalent Nanoarchitectures,” Nature Communications 8 (2017): 14765.

[46] L. Cardenas, R. Gutzler, J. Lipton-Duffin, et al., “Synthesis and Electronic Structure of a Two Dimensional π-Conjugated Polythiophene,” Chemical Science 4, no. 8 (2013): 3263–3268.

[47] W. Liu, X. Luo, Y. Bao, et al., “A Two-Dimensional Conjugated Aromatic Polymer via C─C Coupling Reaction,” Nature Chemistry 9, no. 6 (2017): 563–570.

[48] W. Liu, M. Ulaganathan, I. Abdelwahab, et al., “Two-Dimensional Polymer Synthesized via Solid-State Polymerization for High-Performance Supercapacitors,” ACS Nano 12, no. 1 (2018): 852–860.

[49] Y. Jing and T. Heine, “Two-Dimensional Kagome Lattices Made of Hetero Triangulenes Are Dirac Semimetals or Single-Band Semiconductors,” Journal of the American Chemical Society 141, no. 2 (2018): 743–747.

[50] J. Wang and S. Y. Quek, “Isolated Flat Bands and Physics of Mixed Dimensions in a 2D Covalent Organic Framework,” Nanoscale 12, no. 39 (2020): 20279–20286.

[51] S. Thomas, H. Li, C. Zhong, M. Matsumoto, W. R. Dichtel, and J.-L. Bredas, “Electronic Structure of Two-Dimensional π-Conjugated Covalent Organic Frameworks,” Chemistry of Materials 31, no. 9 (2019): 3051–3065.

[52] H. Geng, L. Zhu, Y. Yi, D. Zhu, and Z. Shuai, “Superexchange Induced Charge Transport in Organic Donor–Acceptor Cocrystals and Copolymers: A Theoretical Perspective,” Chemistry of Materials 31, no. 17 (2019): 6424–6434.

[53] W. Jiang, H. Huang, and F. Liu, “A Lieb-Like Lattice in a Covalent-Organic Framework and Its Stoner Ferromagnetism,” Nature Communications 10, no. 1 (2019): 2207.

[54] X. Ni, H. Li, F. Liu, and J.-L. Brédas, “Engineering of Flat Bands and Dirac Bands in Two-Dimensional Covalent Organic Frameworks (COFs): Relationships Among Molecular Orbital Symmetry, Lattice Symmetry, and Electronic-Structure Characteristics,” Materials Horizons 9, no. 1 (2022): 88–98.

[55] J. Hafner, “Ab-Initio Simulations of Materials Using VASP: Density-Functional Theory and Beyond,” Journal of Computational Chemistry 29, no. 13 (2008): 2044–2078.

[56] G. Kresse and D. Joubert, “From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method,” Physical Review B 59, no. 3 (1999): 1758–1775.

[57] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865–3868.

[58] J. Heyd, G. E. Scuseria, and M. Ernzerhof, “Hybrid Functionals Based on a Screened Coulomb Potential,” Journal of Chemical Physics 118, no. 18 (2003): 8207–8215.

[59] S. Grimme, S. Ehrlich, and L. Goerigk, “Effect of the Damping Function in Dispersion Corrected Density Functional Theory,” Journal of Computational Chemistry 32, no. 7 (2011): 1456–1465.

[60] M. Reguzzoni, A. Fasolino, E. Molinari, and M. C. Righi, “Potential Energy Surface for Graphene on Graphene: Ab Initioderivation, Analytical Description, and Microscopic Interpretation,” Physical Review B 86, no. 24 (2012): 245434.

[61] L. Sarkisov and A. Harrison, “Computational Structure Characterisation Tools in Application to Ordered and Disordered Porous Materials,” Molecular Simulation 37, no. 15 (2011): 1248–1257.

[62] K. Momma and F. Izumi, “VESTA 3 for Three-Dimensional Visualization of Crystal, Volumetric and Morphology Data,” Journal of Applied Crystallography 44, no. 6 (2011): 1272–1276.

[63] J. M. Soler, E. Artacho, J. D. Gale, et al., “The SIESTA Method for ab Initio Order-N Materials Simulation,” Journal of Physics: Condensed Matter 14, no. 11 (2002): 2745–2779.

[64] B. Lukose, A. Kuc, and T. Heine, “The Structure of Layered Covalent-Organic Frameworks,” Chemistry—A European Journal 17, no. 8 (2011): 2388–2392.

[65] E. C. Stoner, “Collective Electron Ferronmagnetism,” Proceedings of the Royal Society A Mathematical Physical and Engineering Sciences 165, no. 922 (1938): 372–414.

[66] E. Jin, M. Asada, Q. Xu, et al., “Two-Dimensional sp² Carbon-Conjugated Covalent Organic Frameworks,” Science 357, no. 6352 (2017): 673–676.

[67] B. Cui, X. Zheng, J. Wang, D. Liu, S. Xie, and B. Huang, “Realization of Lieb Lattice in Covalent-Organic Frameworks With Tunable Topology and Magnetism,” Nature Communications 11, no. 1 (2020): 66.

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